110
SOXE N E W SALTS O F A L P H A T I I Y M O L E SULPI10-ACID.
Ui7,ectors I. Jii31Es 33. STEBBISR, JR., ll. MORTON, 1’. C A S A M A J O K , C. F. CIIASDLER, M. ALSBERG, E. R. SQEIBB, w. ir. K ~ JV.~31. I L ~~D I R S H~~ ~ ~ ~ , ~ELWYN ~WALLER, ~ ~ H.ENDEMASS, A. R.G A r . r . A r r x , GEO.PKOCIIAZKA, A. 11. T,ICEDS. * I s the Cliairinan was ubliged to depart before the close of meeting, Mr. CASAMAJOB was electcd Chairman pi80 fern. T h e meeting was tlleii adjourned.
JAlllES I€. STEBBINS, JR., Becording Secretary.
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xxvIII.-oX AND
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S O M E S E W S A L T S O F ALPHA THYMOLE SULPHO-ACID, SOMENEWFACTS CONCERNING THE SAME.
(Second Paper )
BY J.i>fES H STEBBIXS, Jn. In my last paper I described the calcium and ammonium salts of alpha thymole sulpho-acid. In this paper I will describe the sodium salt and free sulpho acid, which I mentioned in connection with m y first paper. Soda salt of alpha thymole sulplio-acid, C,H,(CII,) (CsH,)(NaSOs)ONa 2+€120. A part of the lime salt was dissolved in boiling water aiid decomposed with Na2C0,. T h e CaCO, thus formed was then filtered off, and the clear filtrate concentrated over the steam bath to the consistency of a syrup. On cooling, the soda salt crystallized in fine white, rhombic plates, with strong vitreous lustre. These crystals show the planes, a: mc: cab, or macropinacoids ; and mc : b : J) a, or macrodomes. The crystalline form may be seen from the following diagram:
+
111
S O M E NEW SALTS OF ALPHA THYMOLE SULPHO-ACID.
This compwnd is easily soluble in water and alcohol; melting point, 166 to 16'7OC. A t 10o°C., i t parts with all its water of crystallization, and crumbles into a fine white powder, in the same manner a8 the other salts described. Alpha thymole su@ho-ncid: C,R,(CII,)(C,H,)(HSO,)OH + H,O. It was first tried to obtain this body by decomposing the lime salt with CO, ; however, this failed completely, as eveu a prolonged passing of CO, through a concentrated solution of the lime salt failed to produce the slightest precipitate of carbonate of lime. Therefore, this was abandoned, and the lead salt was resorted to, as the best means of accomplishing this end. 60 grms. of thymole were dissolved in 50 grms. of €I,SO,, and heated on the steam bath till the contents of the dish became nearly one crystallized mass. The colorless fluid * remaining was poured off, and the pink crystalline body dissolved in boiling water, and was then neutralized with carbonate of lead. The lead sulphate formed was filtered off, and .z cnrrent of H,S was then passed through the clear filtrate, till all the lead (in combination with thymole sulpho-acid) had been precipitated as black sulphide of lead. This was then collected on a filter, and the filtrate evaporated to the consistency of a syrup. When cold, the fret: sulpho acid crystallized in beautif 111, large white rhombic scales, with pearly lustre and greasy feel. I t dissolves very readily in hot and cold water ; melting point, 91 to 9 2 O c. This body, in crystallizing, retains a certain amount of water, with which i t parts, howerer, if placed for a few days oyer sulphuric acid. A water estimation of substance dried over sulphriric acid gave : 1.052 grm. substance lost 0.15 grm. of water, or equivalent to very nearly one molecule. Heated on platinum foil, the salt first melts and then burns with sooty red flame, leaving a voluminous black carbon residue behind. A carbon and hydrogen estimation of the above gave: THEORY.
C l o . ................... 120 H14.................... 14
s ..................... 0, ....................
32
64
230
............52.1'7 percent.. ............ 6.08 ............ 13.91 . . . . . . . . . . . 2'7.84 "
"
--
"
100.00
*This fluid is the same as mentioned in my first, as a by-product in the preparation of alpha thymole gulpho-acid.
112
D I A Z O C O M P O U N D S WITH A L P H A T H Y M O L E G U I , P H O - A C I D . FOUXD.
Carbon.. . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2 . 1 9 per cent. IIydrogcn.. . . . . . . . . . . . . . . . . . . . 6.10 '' R P PRODUCT
The by-product Iicretofore described was dissolved in boiling water, and neutralizcd with PbCO,. l'hc precipitate of PbSO, was collected on a filter, and the clear filtrate treated with a current of H,S. till all the lead had been thrown down as PbS. This was collected on a filter, and the filtr'ste evaporated to the consistency of a syrup. I t was then placed over SUIphuric acid and allowed to crystallize. T h e compound so obtained crystallizes in long, white needles, which bear a striking resemblance to the disulpho acid of alpha thymole. They are very easily soluble in water, and are likewice quite hygroscopic. Owing to the small amount of substance under examination, a combustion was out of question, but to judge from the appearance of this body, I should immediately call it alpha thymule disulpho-acid ..
xxI~.-O.VT H & OMBI BIN AT ION O F DIAZO cO3IPOUSDS TIIYXOLE SULPHO-ACID. BY JAMESH.
STEBBINS,
WlTH
ALPHA
JH.
I n my last paper I hinted a t the possibility of combining diazo compounds with alpha thymole sulpho-acid, and I will take the liberty, on this occasion, of describing my experiments in this direction. Azobenzole alpha thymole sulpho-acid, C,H, - N = N -- CeH(CII3) (CSH,) (HSO3)OH. 9.3 grms. aniline were dissolved in 22 grms. of strong HCI, diluted with 200 C.C. of water. T o this mixture was then added, under constant stirring, 7 grms. of NaNO,, previously dissolved in 50 C.C. of water. The diazobenzole chloride thus formed was added gradually to an alkaline solution of the soda salt of alpha thymole sulpho-acid, consisting of 23.6 grms. of the sulpho acid and 8 grms. of KOH, previously dissolved in 200 C.C. of water. A copious yellow precipitate, composed of minute hair-fine needles, is thus formed, and constitutes the soda salt of our new dye-stuff. This was then dissolved in boiling water and filtered from a black tarry fluid which was formed during the dissolving procese. This
